CuI-Amidobis(phosphine)-Catalyzed Direct Amidation of Unactivated Alkanes via C(sp3)-H Activation.

Herein, we describe an acid-base-free, sustainable, and efficient method for direct amidation of unactivated alkanes and toluene derivatives, using the dimeric CuI complex [CuI{o-Ph2PC6H4CONC6H4PPh2-o}2] (here onward referred to as [PNP-Cu]2). Using this method, C(sp3)-N bond formation was achieved through the activation of very challenging C(sp3)-H bonds in cycloalkanes, alkenes, allyl groups, and benzyl groups, with tolerance toward ketonic groups, heterocycles, and halide functionalities. One of the precatalysts, (PNHP-Cu-Npht) was isolated and structurally characterized. Isomerization in allyl-functionalized alkanes and selective benzylic alkylation in ketones were observed. This is a novel method for C(sp3)-N bond formation via direct N-alkylation of phthalimide, sulfonamide, benzamide, and phosphamidate.

CuI-amidobis(phosphine) catalyzed C(sp3)-C(sp3) direct homo- and hetero-coupling of unactivated alkanes via C(sp3)-H activation.

Herein, we present a CuI-dimer, [CuI{Ph2PC6H4C(O)NC6H4PPh2-o}]2, which catalyzed direct C(sp3)-H homocoupling of benzyl and cycloalkane derivatives with excellent yields and regio-selectivity. The method is very simple and tolerates various functionalities. Synergistic metal-ligand cooperativity was observed in Cu-N bond cleavage and protonation of nitrogen, and facilitates a bifunctional pathway, minimising the free energy corrugation for catalytic intermediates.

Copper(I) Complexes of Amide Functionalized Bisphosphine: Proximity Enhanced Metal-Ligand Cooperativity and Its Catalytic Advantage in C(sp3)-H Bond Activation of Unactivated Cycloalkanes in Dehydrogenative Carboxylation Reactions.

The reactions of amide functionalized bisphosphine, o-Ph2PC6H4C-(O)N(H)C6H4PPh2-o (1) (BalaHariPhos), with copper salts is described. Treatment of 1 with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{(o-Ph2PC6H4C(O)N(H)C6H4PPh2-o)}-κ2-P,P] (X = Cl, 2; Br, 3; and I, 4), which on subsequent treatment with KOtBu resulted in a dimeric complex [Cu(o-Ph2PC6H4C(O)(N)C6H4PPh2-o)]2 (5). Interestingly, complexes 2-4 showed weak N-H···Cu interactions. These weak H-bonding interactions are studied in detail both experimentally and computationally. Also, CuI complexes 2-5 were employed in the oxidative dehydrogenative carboxylation (ODC) of unactivated cycloalkanes in the presence of carboxylic acids to form the corresponding allylic esters. Among complexes 2-5, halide-free dimeric CuI complex 5 showed excellent metal-ligand cooperativity in the oxidative dehydrogenative carboxylation (ODC) in the presence of carboxylic acids to form the corresponding allylic esters through C(sp3)-H bond activation of unactivated cycloalkanes. Mechanistic details of the catalytic process were established by isolating the precatalyst [Cu{(o-Ph2PC6H4C(O)(NH)C6H4PPh2-o)-κ2-P,P}(OOCPh)] (6) and fully characterized by mass spectrometry, NMR data, and single-crystal X-ray analysis. Density functional theory-based calculations further provided a quantitative understanding of the energetics of a series of H atom transfer steps occurring in the catalytic cycle.

Application of ultrasonication as pre-treatment for freeze drying: An innovative approach for the retention of nutraceutical quality in foods.

Freeze drying (FD) is an important and highly effective technology in food industry for retaining the quality in final dried product. This drying technique is performed at lower temperatures, restricting the damage suffered by thermally sensitive ingredients. However, FD consumes large amount of energy and required more time than conventional drying methods. The utilization of ultrasonic technology (US) as pre-treatment before FD represents a promising alternative in accelerating the drying process, decreases energy consumption and maintaining quality as compared to the non pre-treated sample. This review summarizes research progress and current studies in ultrasonic as pre-treatment for freeze drying (US + FD) technique. The impact of US + FD on phytochemical, color, texture and micro-structure of food are well summarized. The review also suggests that the optimised US treatment parameters are required to improve heat and mass transfer in food samples which help in speed up the drying process and reduction of drying time.

Intraoperative Parameters of Comminuted Proximal Humerus Fractures: A Comparison Between Deltoid-Split and Deltopectoral Approaches.

Background and objective Many controversies exist in the literature regarding proximal humerus fractures treated with various surgical procedures. The chosen approach decides the level of comfort with which the surgeon can perform a particular surgery in orthopedics and the amount of reduction a surgeon can bring to a fractured bone. The purpose of this study was to compare variables such as time taken for surgery, achievement of reduction, and intraoperative blood loss between the two most frequently employed surgical approaches for proximal humerus in comminuted fractures: the deltoid-split (DS) approach and deltopectoral (DP) approach. Methods All patients with Neer III and IV types proximal humerus fractures treated with Proximal Humeral Interlocking System (PHILOS) plating from 2017 to 2020 were invited to participate in the study. The exclusion criteria were as follows: Neer type I and II fractures, pre-existing limb pathology, patient refusal or patient being unfit for surgery, and patient requiring a different modality of treatment like external fixator and pinning. After obtaining consent, the dark envelope method was used to randomize patients into one of the two treatment methods. The variables analyzed were time taken for the surgery, intraoperative blood loss, anatomical reduction in immediate postoperative X-ray, and complications. The results were analyzed and findings were recorded. Results A total of 42 patients were randomized into the two groups (22 DS, 20 DP; mean age of 44.85 years for DS and 49.61 years for DP). In terms of age, gender, and Neer fracture classification, the groups were comparable. The average blood loss estimated was less in the DS group compared to the DP group; however, the difference was not statistically significant. Intraoperative time was not significantly different between the DS and the DP groups. The surgeons were able to achieve a significantly higher anatomical reduction in the immediate postoperative X-ray with the DP approach compared to the DS approach. The complications (two in DS and two in DP) in either approach were equal in number although all of them were unique. Conclusions The proximal humerus fracture treatment with a PHILOS plate is considered to be a reliable option using either of the described approaches. Based on our findings, the choice of the approach has no impact on surgical time and blood loss. However, patients who were operated on with the DP approach fared better in terms of achieving reduction as assessed by immediate postoperative X-ray owing to limited exposure distally limited by the axillary nerve.

Impact of Socioeconomic Factors on Patient's Adherence to Lifestyle Modifications Aimed at Reducing Future Fracture Risk in Geriatric Patients With Peritrochanteric Fragility Fractures of the Hip.

Introduction A history of fracture is a well-documented risk factor for sustaining future falls and subsequent fractures in geriatric patients. Orthopedic surgeons advocate various lifestyle modifications to reduce the risk of sustaining a recurrent fracture in this vulnerable group. However, it has been observed that patients seldom adhere to this advice and the rate of fragility fractures has thus continued to rise in this vulnerable subset of the population. The factors influencing the compliance of patients with various modifications have not been documented in any previous studies. In our study, we aimed to evaluate the factors influencing patient adherence to various lifestyle modifications advised by orthopedic surgeons for reducing future fracture risk. Material and methods A total of 112 patients aged >65 years who were diagnosed as having a peritrochanteric fragility fracture of the hip and were treated operatively for the same were included in this study. Upon discharge from the hospital, the patients were advised 10 lifestyle modifications to reduce the recurrent fracture risk. A data collecting form that graded the adherence on a 20-point scale (2 points for each lifestyle modification) was prepared by the investigators. Upon the six-month follow-up visit, adherence was assessed on the 20-point scale, and data were collected via the face-to-face interview method. Statistical analysis was accomplished by the Chi-square test and logistic regression analysis. Observations and results Of the 112 subjects included in the study, 58 (51.7%) were male and the mean age was 75 ± 8 (65 - 92) years. The adherence to less than 4 recommendations (Score <8) was seen in 39.2%, adherence to 4 - 6 recommendations (Score between 8 - 12) was seen in 30.86%, adherence to 6 - 8 recommendations (Score between 12 and 16) was seen in 29.94% and adherence to eight to 10 recommendations (score between 16 and 20) was seen in 0% of participants. According to the regression analysis, the presence of adherence to less than six recommendations was related to the low-income level (OR=0.298; 95%CI - 0.132-0.666; p<0.001) and lack of education and awareness (OR=2.329; 95% CI - 1.114-4.859; p=0.002). Conclusion The rates of adherence to advised lifestyle modifications were generally found to be low. Compliance was particularly reduced in patients belonging to the lower socioeconomic strata, which were less likely to be educated and had lower rates of income. The authors concluded that merely advising lifestyle modifications was not enough, and various social and public health measures are required to improve patient compliance, with the broader aim of ending the menace of recurrent fragility fractures.

Recent advances in the technology of chapatti: an Indian traditional unleavened flatbread.

Chapatti is a flattened circular flatbread also known as roti, poli, safari, and phulka, usually baked on a hot iron griddle. It is a staple diet of India and hence the quality of chapatti plays a major role in its acceptance. The overall quality of chapatti is dependent on various attributes such as pliability, handfeel, chapatti eating quality, and taste. These attributes are influenced by numerous factors, including wheat genotypes, wheat varieties, the molecular weight distribution of proteins, and processing techniques. This staple food has been extensively studied for various aspects, including processing, mechanism, fractionation, and reconstitution, quality improver, shelf life extension and also the mechanization of processing. This review focus on all the above-mentioned aspects and innovations carried out in this area.

Chemometric approach-based characterization and screening of gluten free flours for development of Indian unleavened flatbread.

The objective of the study was to screen amongst various gluten free flours to prepare Indian unleavened flatbread using principal component analysis (PCA) and hierarchical cluster analysis (HCA) as a mathematical tool. Gluten free flours studied in this work were, rice, sorghum, moong, amaranth, sama, ragi, water chestnut, buckwheat, soy, tamatind kernel, chickpea, black gram and unripe banana flour. The characteristics of sorghum: rice flatbread was analyzed such as dough making ability, subjective rollability, puffing and acceptability with respect to wheat. Interrelationship between the parameters analyzed and the different gluten free flours were investigated by using PCA and HCA. PCA revealed that the first two components represented 92.56% of the total variability in flatbread making characteristics. HCA classified samples into 6 clusters on the basis of measured flatbread making characteristics. From the results, moong, water chestnut and unripe banana flour in addition to mixture sorghum: rice (30:70) flour were chosen as ingredients for the preparation of Indian unleavened flatbread.

A comprehensive overview of functional and rheological properties of aloe vera and its application in foods.

Aloe vera catches attention of food industry due to its various health benefits like emollient, anti-inflammatory, purgative, anti-microbial, aphrodisiac, antifungal, and antioxidant. Aloe vera gel has excellent functional and nutritional properties and its incorporation into food can increase its functional and nutritional value of the food. However, both the pulp and aloe gel contain a lot of insoluble polymer particles, which affect the rheological behaviour and physical stability mechanisms of the suspensions during storage and processing. While many researchers have explored the application of aloe vera juice in the food products, no literature review of food applications of aloe vera along with their rheological properties have been complied. Hence, the present review aimed to focus on the utilization of aloe vera in the various sectors of food processing and gives insights on the rheological and flow behaviour of aloe vera juice which is a critical parameter for its food application.

Pasting, viscoelastic and rheological characterization of gluten free (cereals, legume and underutilized) flours with reference to wheat flour.

In this study, the rheological properties of dough prepared from gluten free flours (rice, sorghum, moong, water chestnut and unripe banana) and wheat dough were determined. Pasting properties and viscoelastic properties were analyzed using rheometer and dough rheology experiment was performed on texture analyzer. Water chestnut flour exhibited highest peak viscocity (22.6 Pa s), trough viscosity (12.1), breakdown viscosity (10.5 Pa s) and final viscosity (14.92 Pa s) than others while unripe banana flour showed highest setback viscosity (4.54 Pa s). Pasting temperature was found to be highest for sorghum followed by wheat and others. The highest elastic (G') and loss (G″) module were obtained for moong flour. Wheat and gluten free flours were found to exhibit thixotropic effect. Moong flour dough was found to be the stickiest (dough stickiness 57.83 g) followed by WCF, UBF, wheat, rice and sorghum. Similar trend was observed for dough strength. These flours can be proved as key materials for the gluten-free products market and can provide additional inexpensive advantage to the food processing industry.

Non-thermal plasma: An advanced technology for food industry.

In this era of green technology, plasma technology is one of the novel techniques intended towards many industries including food industry as a principal application due to less utilization of energy, solvents, and water with minimum impact on food quality. The foremost purpose behind the utilization of nonthermal plasma processing (cold plasma) lies in the retention of freshness of food products along with furtherance of sensory properties as well as functional and nutritional composition. In addition, this technique assists in shelf life extension and carries out desirable modifications in the structure of food and packaging material. This technology has been proven to be advantageous over other technologies since all these processes are carried out at low temperature, hence is highly suitable for heat-sensitive materials. The present review summarizes the mechanism of this plasma technology along with its benefits to the industry, for example improvements in cooking quality, enhancements in enzyme activity, modification of starches, and microbial inactivation. Also, the effects of plasma treatment on characteristics of various food products have been elaborated in this review.

Novel, energy efficient and green cloud point extraction: technology and applications in food processing.

Recently, a novel technique for extraction of functional thermally sensitive bioactive components from food has been developed due to its green efficacy (no toxic chemicals) and cost effectiveness. Cloud point extraction (CPE) is one of the such best alternative techniques that can be used for extraction of wide range of organic and inorganic components using green surfactants. It is a simple, rapid and inexpensive extraction technique which involves clustering of non-ionic surfactant monomers to form a hydrophobic core (micelle), which then entraps the hydrophobic bioactive compounds within it. CPE can be applied for extraction of bioactives from food processing waste as well as separation and purification of proteins. Besides that, research has received special attention on sample preparation for analysis of food constituents in the last decade. The scope of CPE is very vast in these sectors because of the advantages of CPE over other methods. This review deals with significance of CPE method and their potential green applications in food processing.

Bioactive characteristics and optimization of tamarind seed protein hydrolysate for antioxidant-rich food formulations.

Tamarind seed has been a source of valuable nutrients such as protein (contains high amount of many essential amino acids), essential fatty acids, and minerals which are recognized as additive to develop perfect balanced functional foods. The objective of present work was to optimize the process parameters for extraction and hydrolysis of protein from tamarind seeds. Papain-derived hydrolysates showed a maximum degree of hydrolysis (39.49%) and radical scavenging activity (42.92 ± 2.83%) at optimized conditions such as enzyme-to-substrate ratio (1:5), hydrolysis time (3 h), hydrolysis temperature (65 °C), and pH 6. From this study, papain hydrolysate can be considered as good source of natural antioxidants in developing food formulations.

Bioactive L acidissima protein hydrolysates using Box-Behnken design.

This study examines the extraction and hydrolysis of proteins using single factor and Box-Behnken Design (BBD). From single factor tests, optimised extraction parameters were 1% alkali concentration, 40 °C temperature, 60 min time, and 1:20 solid to alkali ratio. Under these conditions; 924.31 mg/g of total protein was obtained from Limonia acidissima (L acidissima). The maximum degree of hydrolysis was 39.82% at pH 2, enzyme to substrate ratio 2.5% (w/w), and hydrolysis time was 42.41 min using BBD design. L acidissima seed protein hydrolysate showed 32.94% DPPH and 88.18% of ABTS activity at concentration of 100 µg/ml and 1 mg/ml, respectively. Reducing power of 0.16 and metal chelating activity of 87.39% was obtained from 5 mg/ml protein hydrolysates. This implied that L acidissima seed protein hydrolysate could be utilised in protein rich product or as protein supplements.